Molecular science for artificial photosynthesis From bio-inspired catalyst to nanomaterials
V. Artero
Laboratoire de Chimie et Biologie des Métaux,
Université Joseph Fourier, CNRS, CEA Grenoble
www.solhycat.com
23 SEPTEMBRE 2013
Acknowledgements
Marc Fontecave
Murielle Chavarot-Kerlidou
Jennifer Fize
PhD students
Nicolas Queyriaux
Nicolas Kaeffer
Marine Bacchi
Sigolène Canaguier
Romain Métayé
Yohan Oudart
Post-docs Carole Baffert
Aziz Fihri
Pierre-André Jacques
Alan Le Goff
Mathieu Razavet
Phong Tran Dinh
Vincent Fourmond
Saioa Cobo
Eugen S. Andreiadis
Trevor R. Simmons
Gustav Berggren
Collaborations
IBS
Martin Field (DFT)
INAC
Colette Lebrun (ESI-MS)
Jacques Pécaut (X-Ray)
IRAMIS (surface chemistry)
Serge Palacin
Bruno Jousselme
Dalian Univ.of Technology
Licheng Sun
Mei Wang
Zhan Pan
Frei Universität Berlin
Holger Dau
Jonathan Heidkamp
NTU Singapour
Phong. D. Tran
Ibitech-S
Winfried Leibl
LITEN
Nicolas Guillet
Alexandre Pereira
Laure Guetaz
LETI
Murielle Matheron
IPCM- Univ. Paris 6
Anna Proust
Guillaume Izzet
LCMCP- Univ. Paris 6
Christel Laberty-Robert
Clément Sanchez
23 SEPTEMBRE 2013 TW
0 10 20 30
Solar influx on Earth = 120 000 TW
~1h corresponds to our yearly consumption
40
80%
Fossil
Solar per hour
2010; ca 17 TW
The global energy challenge
Annual global photosynthesis ca 125 TW
Nuclear Biomass
Hydro others
Electricity 17%
2050; ca 30 TW Fossil
Fuel 83% Need for chemical
energy storage
23 SEPTEMBRE 2013
Renewable energy: Solar
- Concentration
- Storage (fuels)
Hydrogen (H2)
production
CO2 recycling and
production of liquid fuels
Li-ion batteries: 0.46 - 0.72 MJ.kg-1
Oil: 47 MJ.kg-1
Hydrogen: 140 MJ.kg-1
Renewable energy
SOLAR FUELS
23 SEPTEMBRE 2013
Natural photosynthesis Photovoltaic device PV + electrolysis
Converting solar energy into chemical energy
State of the art « PV + Electrolysis » technology
Photo-Electrochemical Cell
23 SEPTEMBRE 2013
Wired PV + Electrolysis
Nocera Science 2011
Robust- Mature (>18%)
3 devices
PV
Electrolysis cell
Power management
Unwired PV + Electrolysis
Single device
Stability of PV materials into electrolyte
One fixed operating point
PV + electrolysis
Janssen Adv. Mater. 2013 Peharz IJHE 2007
h= 7.8%
7200 h
Turner Science 1998
SOLAR FUELS
23 SEPTEMBRE 2013
Microalgae
H2O
H2
Natural photosynthesis Photovoltaic device PV + electrolysis
Converting solar energy into chemical energy
Sustainability
Economic viability
Abundant and cheap materials both
for light harvesting and catalysis State of the art « PV + Electrolysis » technology
Photo-Electrochemical Cell Artificial photosynthesis
Fundamental research to TRL 2
23 SEPTEMBRE 2013
Solar Fuels: a transversal field
2H2O
O2+ 4H+
a-Fe2O3
Mn
Co
Solid-state materials
Mn
P
Mn
Mn Mn
O2 H2O
Photosynthesis
Biosciences
Molecular chemistry
Nanosciences
H+
H2
: an international initiative
Driven academic research will lead to
simultaneous industry R&D and
commercially-viable products
www.solar-fuels.org
The product: a solar liquid fuel
The method: being global and harness
the intellectual firepower of
government-funded research
institutions and R&D industry
The tools: workshops
map of knowledge
fellow-exchange programs
translational prize (grants)
Light capture
Water splitting
CO2 catalysis
AMPEA : a Joint program of the
European Energy Research Alliance
Advanced Materials and Processes for Energy Applications
43 participant/associate institutions
14 EU countries
This JP is structured as a matrix with 3 “tools” sub-programmes:
SP1 : Materials Science.
SP2 : Characterization of materials and processes.
SP3 : Modelling of materials and processes
and “emerging applications,” among which
Artificial Photosynthesis appears as a first objective
Current activities in Artificial Photosynthesis might
be grouped into three subfields:
• molecularly designed systems
• solid-state components
• nature-guided design
Thapper et al., Green 2013, 3, 43.
23 SEPTEMBRE 2013
CM 1202 “Perspect-H20”: a COST Action
on Supramolecular water splitting:
•fundamental understanding of the function determining light-induced elementary
reactions in supramolecular photocatalytic water-splitting
•novel water-splitting supramolecular photocatalysts
•innovative functional systems operating in solutions, membranes or at surfaces
Working groups
1. Synthesis and Photocatalysis
2. Device Integration
3. Photoinduced Dynamics
4. Intermediates & Active Species
www.perspect-h2o.eu
21 countries
55 research groups
Chair: Dr Benjamin Dietzek, IPHT-JENA
23 SEPTEMBRE 2013
1. Conversion of light energy
into electrochemical potential
Photon absorption and initial charge
separation is achieved by molecular
photosensitizers
Spatial charge separation through a
cascade of electron transfers
Dye-sensitized solar cells (Grätzel cells)
Organic photovoltaics
1.0µm
2. Efficient multielectron
enzymatic catalysis
Fast
Close to the thermodynamic
equilibrium (limited energetic loss)
Photosynthesis
micro-algae
The biomimetic approach
NiFe hydrogenases
H+
H2
Canaguier et al. Chem. Commun 2010, 46, 5876
CODH and formate reductase CaMn4 Cluster (OEC) FeFe and NiFe hydrogenases
Bio-inspiration: Cobaloxime and cobalt
dioxime-dioxime catalysts
E. S. Andreiadis et al. Nature Chemistry, 2013
also valid for with Ni catalysts (Le Goff et al. Science 2009)
Jacques et al, PNAS 2009
Bhattacharjee et al. Chem. Eur. J. 2013
Molecular engineering of a cobalt-based
electrocatalytic nanomaterial for H2 evolution
under fully aqueous conditions
>55 0000 TONs
pH 4.5 acetate buffer
300 mV overpotential
H+
½ H2
e-
Et3N
Et3N•+
>100 turnovers
Cobaloxime-based supramolecular
photocatalysts
Fihri et al. Angew. Chem. Int. Ed. 2008
Review article
Artero, Chavarot-Kerlidou, Fontecave, Angew. Chem. Int. Ed. 2011
Single light-driven electron transfer (ps-ns)
Bi-electronic catalysis (µs-ms)
Charge photoaccumulation : towards
improved systems
Collab. G. Izzet A. Proust, IPCM, Univ Paris 6 Energy Environ. Sci. 2013, 6, 1504
Et3N
Et3N•+
e-
Et3N
Et3N•+
e-
6-7-8-
H+
½ H2
NP ?
Polyoxometallate:
electron reservoir
Towards Dye-Sensitized Photo-
Electrosynthetic Cells (DSPEC)
e-
Photoanode material
H2 O2
PEC cells use renewable ressources (water) to sustainably
produce a fuel (H2) and store renewable energy (sunlight) T. J. Meyer, Nature Chemistry 2011
surface
photocatalyst
N. Lewis, Chem. Rev 2010
Towards Dye-Sensitized Photo-
Electrosynthetic Cells (DSPEC)
Photocathode
Licheng Sun and coll. Chem.
Comm. 2012
Photocathode
Yiying Wu and coll. JACS 2013
e-
h+
Photoanode
Licheng Sun and coll. JACS. 2013
Combining Organic Photovoltaics with water
splitting catalysis
Collab. B. Jousselme, S. Palacin CEA-Saclay
Energy Environ. Sci. 2013, 6, 2706
1N aq. H2SO4
~600 mV photopotential
~200 mV overpotential
MoS3/TiO2
Progresses towards a mature hydrogen economy depends on
breakthroughs in finding new catalytic materials
Biological systems provide the synthetic chemist with both challenges
and inspiration regarding the design of new and efficient catalytic
systems.
One of nature's most fundamental processes – photosynthesis – holds
promises for turning the sun's energy into fuels.
Combining the bio-inspired approach with nanochemical tools, new and
stable energy conversion materials based on earth-abundant elements
can be derived.
Conclusion